Lithium secondary battery with suppressed decomposition of electrolytic solution and preparation method thereof

ABSTRACT

Provided are a lithium secondary battery with suppressed decomposition of an electrolytic solution, and a preparation method thereof. The lithium secondary battery includes a current collector, a cathode and an anode having each active material layer formed on the current collector, and a polymer electrolyte interposed between the cathode and the anode. In the lithium secondary battery, a fluorine resin film is formed on at least one surface of the active material layers of the cathode and the anode. A fluorine resin exists in pores between constituents contained in at least one active material layer of the cathode and the anode. The polymer electrolyte is a polymerized product of a crosslinking monomer and an electrolytic solution including a lithium salt and an organic solvent. Also, a porous membrane made of an insulating resin is interposed between the cathode and the anode.

BACKGROUND OF THE INVENTION

This application claims the priority of Korean Patent Application No.2002-27598 filed on May 18, 2002, which is incorporated herein in itsentirety by reference.

1. Field of the Invention

. The present invention relates to a lithium secondary battery andpreparation methods thereof, and more particularly, to a lithiumsecondary battery with improved lifetime and capacity characteristics bysuppressing a reaction between propylene carbonate (PC) and carbon aselectrolyte constituents.

2. Description of the Related Art

In recent years, according to progress of portable electronic appliancesand wireless communication systems, there has been increasing demandsfor highly reliable, high-performance batteries. Also, for solvingproblems of energy and environmental requirements, development ofsecondary batteries as large power sources for realizing electromotivevehicles and effectively utilizing night electricity, has becomeincreasingly demanded. Among these secondary batteries, lithiumsecondary batteries are drawing particular attention because of theirgood properties such as high operation voltage and high energy density.

Lithium secondary batteries are classified into lithium-ion secondarybatteries using an aqueous electrolytic solution and lithium polymerbatteries using a solid-type electrolytic solution. The lithium ionbattery has problems, such as leakage of an electrolytic solution whilein use. Thus, vigorous research into lithium polymer batteries which areleak-tight and flexibly packaged in a desired shape and can be formed ina large scale has recently been made.

Lithium polymer batteries are expected to solve various problems withlithium ion batteries using a liquid electrolytic solution such as lowsafety, high cost or disadvantage in attaining large-scale, highcapacity batteries. However, in order to solve the above-describedproblems, lithium polymer batteries must satisfy various requirementssuch as stability over a wide voltage range so as to withstandovercharge/overdischarge, high ionic conductivity and chemical,electrochemical compatibility with electrode materials or othermaterials present in a cell.

Japanese Laid-Open Patent Nos. 7-134980, 7-235328 and 9-219188 disclosean anode preparation technique using electrode slurry prepared by mixinga carbon material and a polymer electrolyte in manufacturing an anode.According to this technique, a conduction path of electricity may beclosed, the internal resistance of an electrode is disadvantageouslyhigh and the energy density per unit area is reduced.

Japanese Laid-Open Patent No. 10-284131 discloses a lithium secondarybattery with a path of a gel-type electrolytic solution provided in anactive material by adding a polymer to active material powder. Inelectrodes of the lithium secondary battery disclosed herein, lots ofpores are present between electrode active materials, lowering a bindingforce between the active materials and exhibiting poor batteryperformance in view of uniformity and distribution of pores.

Japanese Laid-Open Patent No. 8-306353 discloses a technique in whichalkali metal containing polymers such as polyethylene oxide (PEO) orpolypropylene oxide (PPO) are applied onto electrode surfaces andcrosslinked. However, such polymers present several problems, that is,they may be dissolved in an electrolytic solution after crosslinkagebecause of their own properties and the electrolytic solution mayinfiltrate into electrodes.

Lithium polymer batteries are classified, depending upon the kind of theelectrolyte used therein, into a solid type containing no organicelectrolytic solution, and a gel type containing an organic electrolyticsolution.

A gel type electrolyte forms a stable gel with a polymer host structureby adding, in excess, an electrolytic solution into a polymer matrix.Although the gel type electrolyte has higher ionic conductivity at roomtemperature than a completely solid polymeric electrolyte, it is ratherpoor in mechanical characteristic. Examples of an organic solvent usefulto form the electrolytic solution include ethylene carbonate (EC) andpropylene carbonate (PC). In particular, PC having a high boiling pointis essentially necessary for crosslinkage for forming a gel-type polymerelectrolyte.

However, PC may be decomposed by reacting with carbon as an anodematerial to produce a gas, resulting in swelling and deterioration ofcycle characteristics.

SUMMARY OF THE INVENTION

To solve the above-described problems, the present invention provides anelectrode for a lithium secondary battery capable of effectivelysuppressing decomposition of an electrolytic solution, particularlypropylene carbonate, and having an improved binding force between theelectrode and a polymer electrolyte, a lithium secondary batteryemploying the electrode, and a preparation method thereof.

In an aspect of the present invention, there is provided an electrodefor a lithium secondary battery comprising a current collector and anactive material layer formed on the current collector, wherein afluorine resin film is formed on the active material layer, and afluorine resin exists in pores between constituents contained in theactive material layer.

The active material layer may include an active material and aconductive agent, and the fluorine resin exists between the activematerial and the conductive agent and on surfaces of the active materialand the conductive agent.

The fluorine resin includes at least one selected from the groupconsisting of vinylidenefluoride-hexafluoropropylene (VdF-HFP) copolymerand polyvinylidenefluoride, and is prepared by coating a compositioncontaining a low-concentration fluorine resin and drying the resultantproduct. Here, the composition preferably contains 0.5 to 7 parts byweight of fluorine resin and 93 to 99.5 parts by weight of an organicsolvent.

In accordance with another aspect of the present invention, there isprovided a lithium secondary battery comprising a current collector, acathode and an anode having each active material layer formed on thecurrent collector, and a polymer electrolyte interposed between thecathode and the anode, wherein a fluorine resin film is formed on atleast one surface of the active material layers of the cathode and theanode, a fluorine resin exists in pores between constituents containedin at least one active material layer of the cathode and the anode, thepolymer electrolyte is a polymerized product of a crosslinking monomerand an electrolytic solution including a lithium salt and an organicsolvent, and a porous membrane made of an insulating resin is interposedbetween the cathode and the anode.

The active material layer may include an active material and aconductive agent, and the fluorine resin exists between the activematerial and the conductive agent and on surfaces of the active materialand the conductive agent.

In an embodiment of the present invention, the porous membrane is acellulose non-woven fabric, a vinylidenefluoride-hexafluoropropylene(VdF-HFP) copolymer film, a polyethylene film, a polypropylene film, adouble layer of polyethylene/polypropylene or a triple layer ofpolypropylene/polyethylene/polypropylene.

The thickness of the fluorine resin film is preferably in the range of0.5 to 10 μm.

The crosslinking monomer is at least one selected from the groupconsisting of hexyl acrylate, butyl acrylate, trimethylolpropanetriacrylate (TMPTA), butanediol dimethacrylate, diallylsuberate,ethylene glycol dimethacrylate, poly(ethyleneglycol) dimethylacrylate,diglycidyl ester, acrylamide and divinyl benzene.

In the present invention, the lithium secondary battery may furtherinclude at least one second crosslinking monomer as the compound capableof crosslinking with the crosslinking monomer, the second crosslinkingmonomer being at least one selected from the group consisting ofpolyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile,acrylonitrile-methylmethacrylate-styrene terpolymer, and vinylene resinsuch as vinyl acetate, 2-vinyl-2,3-dioxolane, acrylomorphorine andvinylmethacrylate.

According to still another aspect, the present invention provides amethod of preparing a lithium secondary battery including (a) coating acomposition containing a fluorine resin and an organic solvent so that afluorine resin film is formed on at least one surface of active materiallayers of a cathode and an anode, the fluorine resin exists in poresbetween constituents contained in at least one active material layer ofthe cathode and the anode, and drying the coated product, (b)interposing a porous membrane made of an insulating resin between thecathode and the anode to form an electrode assembly, (c) accommodatingthe electrode assembly into a battery case and injecting a polymerelectrolyte composition containing a crosslinking monomer and anelectrolytic solution including a lithium salt an organic solvent intothe battery case, and (d) polymerizing the product of the step (c).

In step (a), the active material layer may include an active materialand a conductive agent and the fluorine resin exists between the activematerial and the conductive agent and on surfaces of the active materialand the conductive agent.

The polymer electrolyte composition of step (c) may include 2 to 7 partsby weight of the crosslinking monomer and 93 to 98 parts by weight ofthe electrolytic solution based on the total weight of the composition.

In step (d), polymerization is performed by heating at a temperature inthe range of 60 to 130° C. or radiation by e-beam, γ-beam or UV-ray.

The polymer electrolyte composition of step (c) may further include asecond crosslinking monomer capable of crosslinking with thecrosslinking monomer and the amount of the second crosslinking monomeris in the range of 5 to 20 parts by weight based on the total weight ofthe crosslinking monomer.

Also, the polymer electrolyte composition of step (c) may furtherinclude 1 to 5 parts by weight of a polymerization starter based on thetotal weight of the crosslinking monomer.

BRIEF DESCRIPTION OF THE DRAWINGS

The above objects and advantages of the present invention will becomemore apparent by describing in detail preferred embodiments thereof withreference to the attached drawings in which:

FIG. 1 is a scanning electron microscope (SEM) photograph showing thecross-section of a cathode prepared in Example 2 of the presentinvention;

FIG. 2 is an SEM photograph showing the cross-section of a cathodeprepared in Comparative Example;

FIG. 3 is a graphical representation of cycle characteristics of lithiumsecondary batteries prepared in Example 2 and Comparative Example; and

FIG. 4 is a graphical representation of high-temperature storagecharacteristics of lithium secondary batteries prepared in Example 1 andComparative Example.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, an electrode surface is coated with a fluorineresin film composition containing a low-concentration fluorine resin andan organic solvent and dried to form a fluorine resin film on theelectrode surface, with the fluorine resin existing in pores amongconstituents of an electrode, specifically electrode active materiallayer, preferably between the electrode active material and a conductiveagent and on the surfaces of the electrode active material and theconductive agent, to suppress a direct contact between the electrode andthe electrolytic solution, thereby effectively suppressing decompositionof propylene carbonate (PC). In more detail, if an electrode,specifically an anode, is coated with a fluorine resin film, thefluorine resin film infiltrates into the anode through pores formed inthe anode, thereby forming a fluorine resin film on the surface ofcarbon present in the anode. If the fluorine resin film is coated on thecarbon surface in such a manner, decomposition of PC is suppressed orminimized due to a reaction between carbon and an electrolytic solution,and the binding force between the electrode and the polymer electrolyteis increased to thus reduce interface resistance therebetween. Also,there are several advantages of a shortened crosslinking time forforming a gel-type polymer electrolyte and a lowered crosslinkingtemperature.

The fluorine resin is contained in the composition for forming thefluorine resin film at a low concentration, that is, 0.5 to 7 parts byweight, preferably 1 to 3 parts by weight, based on 100 parts by weightof the composition. If the amount of the fluorine resin is greater than7 parts, the fluorine resin film formed on the electrode surface isexcessively thick. If the amount of the fluorine resin is less than 0.5parts, it is difficult to uniformly coat fluorine resin. Examples of thefluorine resin used to form the fluorine resin film include at least oneselected from the group consisting of avinylidenefluoride-hexafluoropropylene copolymer andpolyvinylidenefluoride, preferably avinylidenefluoride-hexafluoropropylene copolymer. In the copolymer, theamount of a hexafluoropropylene repeating unit is preferably in therange of 10 to 15% by weight. The amount of a vinylidenefluoriderepeating unit is preferably in the range of 85 to 90% by weight, andthe weight average molecular weight thereof is preferably 300,000 to600,000. Any solvent that can dissolve the fluorine resin can be usefulas the organic solvent, and examples thereof include tetrahydrofuran(THF), acetone and dimethyl carbonate. The amount of the organic solventused is preferably in the range of 93 to 99.5 parts by weight based on100 parts by weight of the composition for forming the fluorine resinfilm. If the amount of the organic solvent is less than 93 parts, thefluorine resin film formed on the electrode surface is overly thick toincrease interface resistance. If the amount of the organic solvent isgreater than 99.5 parts, the fluorine resin cannot uniformly infiltrateinto or be uniformly applied onto the electrode, which is undesirable.

The thickness of the fluorine resin film is preferably in the range of0.5 to 10 μm. If the thickness of the fluorine resin is greater than 10μm, the fluorine resin film acts as a resistor, thereby lowering ionicconductivity of the battery. If the thickness of the fluorine resin isless than 0.5 μm, the decomposition suppressing effect of theelectrolytic solution is undesirably small.

A method of preparing a lithium secondary battery according to thepresent invention will now be described.

First, an electrode active material layer is formed on a currentcollector using an electrode active material composition containing anelectrode active material, a binder, a conductive agent and a solvent.Here, the formation method of the electrode active material layerinclude directly coating an electrode active material composition on acurrent collector, coating an electrode active material composition on aseparate support member current collector, followed by drying theresultant structure, and laminating a film stripped from the supportmember. Any material that supports the active material layer can be usedas the support member, and concrete examples thereof include a mylarfilm and a polyethyleneterephthalate (PET) film. Examples of the currentcollector include, but not particularly limited to, a foil, an expandedmetal mesh and a punched metal. A metal film itself can be used as acurrent collector for an anode.

In the present invention, a lithium metal composite oxide such as LiCoO₂or LiMn₂O₄ or a sulfur compound is used as a cathode active material,and a carbon material or graphite such as mesocarbon microbead (MCMB),mesocarbon fiber (MCF) or PHS (commercially available from Japan CarbonCo.) is used as an anode active material. Examples of the conductiveagent include carbon black such as MCMB, MCF, Super-P or acetyleneblack. Here, the conductive agent is preferably used in an amount of 1to 20 parts by weight based on 100 parts by weight of the electrodeactive material.

Examples of the binder include a vinylidenefluoride-hexafluoropropylene(VdF-HFP) copolymer, polyvinylidenefluoride, polyacrylonitrile,polymethacrylate or mixtures thereof. Here, the content of the binder is5 to 30 parts by weight based on 100 parts by weight of the electrodeactive material.

As the solvent, any solvent useful for typical lithium secondarybatteries can be used, and examples thereof include acetone andN-methylpyrrolidone (NMP).

To enhance battery performance, Li₂CO₃ may be further added to theelectrode active material composition.

As described above, a cathode and an anode are prepared by known methodsemployed for manufacturing a general lithium secondary battery.

Then, the fluorine resin film composition is coated on the cathodeand/or anode and vacuum dried. Here, the drying temperature ispreferably in the range of 60 to 80° C., more preferably at 70° C.

A porous membrane made of an insulating resin sheet having a networkstructure is interposed between the thus obtained cathode and anode andwound or stacked, thereby forming an electrode assembly. In the casewhere the electrode assembly is formed based on stacking, the cathode, apolymer electrolyte and an anode are sequentially stacked to form a unitcell. By stacking a plurality of unit cells, a high capacity battery canbe attained.

The porous membrane has a supporting property and is interposed betweenthe cathode and the anode for insulating each other and made of aninsulating material having a porosity of not less than 30% so as toimpregnate a non-aqueous organic electrolytic solution. Examples of theinsulating material satisfying these requirements include a cellulosenon-woven fabric, a VdF-HFP copolymer film, a polyethylene film, apolypropylene film, a double layer of polyethylene/polypropylene and atriple layer of polypropylene/polyethylene/polypropylene.

Thereafter, the thus formed electrode assembly is accommodated in anelectrode case. Then, a polymer electrolyte composition is injected intothe electrode case having the electrode assembly. Here, the injection ofthe polymer electrolyte composition is advantageously performed under adecompressed condition.

The obtained resultant structure is subjected to heat treatment to carryout thermal polymerization or photopolymerization by radiation. Theheating temperature for thermal polymerization is preferably in therange of 60 to 130° C., more preferably 70 to 80° C. If the heatingtemperature is lower than 60° C., a monomer or a crosslinking agentpresent in the battery cannot completely participate in a reaction. Ifthe heating temperature is higher than 130° C., decomposition of anelectrolytic solution or deformation of the monomer or crosslinkingagent may undesirably occur due to a high temperature. Forphotopolymerization, e-beam, γ-beam or UV-ray is preferably used.

The polymer electrolyte composition is prepared by mixing a crosslinkingmonomer and an electrolyte solution composed of a lithium salt and anorganic solvent.

In the present invention, the crosslinking monomer has no particularrestriction as to the kind as long as it is a material having at leasttwo double bonds to be crosslinkable by heat or light. Examples of thecrosslinking monomer are at least one selected from the group consistingof diacrylate or triacrylate, such as hexyl acrylate, butyl acrylate ortrimethylolpropane triacrylate (TMPTA); di-methacrylate such asbutanediol dimethacrylate, or trimethacrylate; diallyl ester such asdiallylsuberate or triallyl ester; ethylene glycol dimethacrylate orpoly(ethyleneglycol) dimethylacrylate; diglycidyl ester; acrylamide; anddivinyl benzene. It is preferable to use bi-functional acryl-basedresins which include polyethylene glycol dimethacrylate. The mixtureratio by weight of the crosslinking monomer to the electrolytic solutionis preferably in the range of 1:1 to 1:15. If the weight of thecrosslinking monomer is smaller than the above range, crosslinkingchains length are too short, resulting in leakage of the electrolyticsolution and poor mechanical property. If the weight of crosslinkingmonomer is greater than the above range, a crosslinked polymer matrixbecomes too brittle.

If polymerization is carried out using the crosslinking monomeraccording to the present invention, radicals are first formed at thedouble bonds present at terminals of the crosslinking monomer, and thenthe radicals bond with another polymer to form crosslinkage.

The composition for forming the polymer electrolyte may further includecompounds capable of crosslinking with the crosslinking monomer, thatis, second crosslinking monomers, which are at least one selected fromthe group consisting of polyethylene oxide, polyvinylpyrrolidone,polyacrylonitrile, acrylonitrile-methylmethacrylate-styrene terpolymer,and vinylene resin such as vinyl acetate, 2-vinyl-2,3-dioxolane,acrylomorpholine or vinylmethacrylate.

When the crosslinking monomer is polymerized with the secondcrosslinking monomer, the added second crosslinking monomer furtherincreases the mechanical strength of the finally obtained polymerelectrolyte. The second crosslinking monomer is used in an amount of 5to 20 parts by weight based on the total weight of the crosslinkingmonomer. If the amount of the second crosslinking monomer exceeds theabove range, the ionic conductivity is undesirably reduced.

To promote polymerization of the crosslinking monomer, a thermalpolymerization initiator or photo-polymerization initiator, depending onthe energy source used for a subsequent gelling process, may be furtheradded to the polymer electrolyte composition. As the polymerizationstarter, any starting material that is typically used in the art can beused without particular restriction. Examples of the thermalpolymerization starter include azoisobutyronitrile (AlBN), diacetylperoxide, cumyl peroixide and the like. Examples of thephoto-polymerization starter include AIBN, benzoin benzoyl ethyl ether(BEE) and disulfide. The polymerization starter is preferably used in anamount of 1 to 10 parts by weight based on 100 parts by weight of thecrosslinking monomer.

The electrolytic solution in the composition for forming the polymerelectrolyte includes a lithium salt and an organic solvent, and theamount thereof is preferably in the range of 100 to 1500 parts by weightbased on 100 parts by weight of the crosslinking monomer. If the amountof the electrolytic solution is less than 100 parts, the ionicconductivity of the polymer electrolyte is undesirably lowered. If theamount of the electrolytic solution is greater than 1500 parts, themechanical property of the polymer electrolyte is undesirablydeteriorated.

The lithium salt is at least one selected from the group consisting ofLiClO₄, LiCF₃SO₃, LiPF₆, LiN(CF₃SO₂)₂ and LiBF₄, The organic solvent ispreferably at least one selected from the group consisting of ethylenecarbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC),ethylmethyl carbonate (EMC), dipropyl carbonate, diethoxyethane,dimethoxyethane, γ-butyrolactone, dioxolane and polyethylglycoldimethylether. In particular, in the present invention, EC/DMC/EMC,EC/DMC/EMC/PC, EC/DMC/PC or EC/PC mixtures are used as the electrolyticsolution. The concentration of the lithium salt in the electrolyticsolution is preferably 0.5 to 1.5 M.

The battery according to the present invention is not specificallylimited in view of its case shape, and a cylindrical or rectangular caseand a pouch type case can be used in the present invention. The pouchtype case is advantageously used because a lightweight, high-energydensity battery can be easily manufactured.

If the polymer electrolyte composition is injected into the batterycase, the electrolytic solution is impregnated into an electrode and aporous membrane. However, the crosslinking monomer having a relativelylarge molecular weight cannot impregnated thereinto but remains on thesurface of the electrode and the porous membrane. Heating or radiationinduces crosslinkage between the crosslinking monomers remaining on thesurface of the electrode and the porous membrane or between thecrosslinking monomer and a crosslinkable compound, leading to gelation.

The crosslinkage between the crosslinking monomers or between thecrosslinking monomer and a crosslinkable compound gives rise toformation of a network structure on the surface of the electrode andporous membrane, to prevent the electrolytic solution impregnated intothe porous membrane from leaking out, thereby enhancing a binding forcebetween the electrode and the porous membrane.

The present invention will now be described through the followingexamples and is not limited thereto.

EXAMPLE 1

1 g of Kynar 2801 (produced by Elf Atochem) as a crosslinking monomer(VdF-HFP copolymer mixed in a weight ratio of 88:12) was dissolved in 99g of THF to prepare a fluorine resin film composition. 94 g of LiCoO₂, 3g of Super-P and 3 g of polyvinylidenefluoride (PVDF) were dissolved in80 g of N-methyl-2-pyrrolidone to prepare a cathode active materialslurry. The cathode active material slurry was coated on an aluminum(Al) foil having a width of 4.9 cm and a thickness of 147 μm, followedby drying at 80° C., thereby forming a VdF-HFP copolymer film having athickness of 7 μm on a cathode.

Separately, 90 g of mezophase carbon fiber (MCF) (Petoca Ltd., Japan),10 g of PVDF were dissolved in 80 g of N-methyl-2-pyrrolidone to preparean anode active material slurry. The anode active material slurry wascoated on a copper foil having a width of 5.1 cm and a thickness of 178μm, followed by drying at 90° C., thereby forming a VdF-HFP copolymerfilm having a thickness of 7 μm on an anode.

A porous VdF-HFP film (commercially available in the trade name ofCelgard by Heochest and having a porosity of 30–50%) was interposedbetween the cathode and anode and wound to form an electrode assembly.The electrode assembly was put into a battery case, decompressed andthen a polymer electrolyte composition to be described below wasinjected into the battery case under a decompressed condition. Thepolymer electrolyte composition was prepared by mixing 50 g of anelectrolytic solution containing 1.3M LiPF₆ and EC:DMC:PC in a weightratio of 3:5:2, 7.5 g of polyethylene glycol dimethacrylate and 0.5 g ofAlBN.

Thereafter, the resultant product was cured at 70° C. for approximately15 seconds, thereby completing a lithium secondary battery.

EXAMPLE 2

A lithium secondary battery was completed in the same manner as inExample 1 except that in preparing the fluorine resin film composition,the amounts of Kynar 2801 and THF were changed into 2 g and 98 g,respectively.

EXAMPLES 3–7

Lithium secondary batteries were completed in the same manner as inExample 1 except that in preparing the fluorine resin film composition,the amounts of Kynar 2801 and THF were changed into 3 g and 97 g; 4 gand 96 g; 5 g and 95 g; 6 g and 94 g; and 7 g and 93 g, respectively.

COMPARATIVE EXAMPLE

A lithium secondary battery was completed in the same manner as inExample 1 except that the step of forming VdF-HFP copolymer films byapplying a fluorine resin film composition on surfaces of a cathode andan anode and drying, was not performed and heat treatment for curing wasperformed at 90° C. for 25 seconds.

In the lithium secondary batteries prepared in Example 2 and ComparativeExample, the cross-sections of cathodes were examined by scanningelectron microscope (SEM) and the results thereof are shown in FIGS. 1and 2.

FIG. 1 is a scanning electron microscope (SEM) photograph showing thecross-section of a cathode prepared in Example 2 of the presentinvention, and FIG. 2 is an SEM photograph showing the cross-section ofa cathode prepared in Comparative Example. FIGS. 1 and 2 show the extentof the VdF-HFP copolymer film coated on the electrode and the extent ofthe VdF-HFP copolymer infiltrated into the electrode. Compared to thecathode shown in FIG. 2, the cathode shown in FIG. 1 has the VdF-HFPcopolymer existing between active materials in the electrode. Incontrast, more pores are distributed throughout the cathode shown inFIG. 2 than that shown in FIG. 1.

Cycle characteristics of the lithium secondary batteries prepared inExample 2 and Comparative Example were examined and the results thereofare shown in FIG. 3.

Referring to FIG. 3, after 45 cycles, the lithium secondary batteryprepared in Example 2 was approximately 96% in initial capacityretention whereas the lithium secondary battery prepared in ComparativeExample was approximately 89% in initial capacity retention. Thus, it isconfirmed that formation of a Kynar 2801 film on the electrode improvescapacity and charge/discharge characteristics of a battery.

In the lithium secondary batteries prepared in Examples 1–7 andComparative Example, the swelling and impedance characteristics wereexamined and the results thereof are shown in Table 1. The swellingcharacteristics of the batteries were evaluated by observing a change inbattery thickness, the discharge capacities were measured at a rate of0.2 C, and the impedance characteristic was evaluated by determiningresistance values before and after charging/discharging.

TABLE 1 Amount of Swelling Discharge Kynar 2801 thickness capacityImpedance R (parts byweight) (mm) (mAh) (Ω) Standard —  3.3 320 —Example 1 1 7.15 310  0.6 Example 2 2  5.4 310 0.58 Example 3 3 — 308 —Example 4 4 5.31 289 0.46 Example 5 5 — 276 — Example 6 6 4.73 260 0.33Example 7 7 — 230 — Comparative 0 9.39 315 0.75 Example

In Table 1, the term “standard” denotes the dimension of a battery asdesigned at primarily charged/discharged states.

As can be understood from Table 1, the lithium secondary batteriesprepared in Examples 1–7 had better swelling characteristic and lowerinterface resistance than the lithium secondary battery prepared inComparative Example.

In the lithium secondary batteries prepared in Examples 1–7 andComparative Example, the time and temperature for crosslinkage forforming a polymer electrolyte were examined.

The results showed that the lithium secondary battery prepared inExample 1 had shorter time and lower temperature for crosslinkage thanin Comparative Example, which is attributed to the structural similarityof the polymer coated on surface of the electrodes and the polymerelectrolyte.

In the lithium secondary batteries prepared in Example 1 and ComparativeExample, the high-temperature storage characteristics were examined, andthe results thereof are shown in FIG. 4.

FIG. 4 shows time-dependent heat generated when the batteries werestored at high temperature. Referring to FIG. 4, the lithium secondarybattery prepared in Comparative Example exhibited thermal runaway alongwith an abrupt exothermic reaction after 400 minutes. On the other hand,the lithium secondary battery prepared in Example 1 exhibited no thermalrunaway and an exothermic reaction slightly occurred after approximately1200 minutes.

The present invention has the following advantages.

First, a fluorine resin such as VdF-HFP copolymer is coated on anelectrode surface, particularly an anode surface, so that the copolymerinfiltrates into pores in the electrode to suppress a direct contactbetween carbon of the anode and propylene carbonate of an electrolyticsolution even during injection of the electrolytic solution, therebyeffectively suppressing decomposition of PC.

Second, since the decomposition between carbon and PC is suppressed,relatively cheap carbon materials such as KCF, mesocarbon fiber (MCF) orPHS can replace expensive mesocarbon microbead (MCMB), thereby reducingthe manufacturing cost.

Third, a binding force between an electrode and a gel-type polymerelectrolyte is increased.

Fourth, compared to the manufacture of conventional gel-type polymerelectrolytes, the time and temperature required for crosslinkage forforming a gel-type polymer electrolyte according to the presentinvention can be reduced.

Fifth, use of a porous membrane in addition to the gel-type polymerelectrolyte can increase the mechanical strength of the gel-type polymerelectrolyte.

Sixth, enhanced thermal stability of the lithium secondary batteryaccording to the present invention leads to an increase inhigh-temperature stability, and cycle life characteristics thereof canalso be improved.

1. A lithium secondary battery comprising: a current collector, acathode and an anode having each active material layer formed on thecurrent collector; and a polymer electrolyte interposed between thecathode and the anode, wherein a fluorine resin exists in pores betweenconstituents contained in at least one active material layer of thecathode and the anode, the polymer electrolyte is a polymerized productof a crosslinking monomer and an electrolytic solution including alithium salt and an organic solvent, and a porous membrane made of aninsulating resin is interposed between the cathode and the anode, andwherein the crosslinking monomer is at least one selected from the groupconsisting of hexyl acrylate, butyl acrylate, trimethylolpropanetriacrylate (TMPTA), butanediol dimethacrylate, diallylsuberate,ethylene glycol dimethacrylate, poly(ethyleneglycol) dimethylacrylate,diglycidyl ester, acrylamide and divinyl benzene.
 2. The lithiumsecondary battery according to claim 1, wherein the active materiallayer includes an active material and a conductive agent, and thefluorine resin exists between the active material and the conductiveagent and on surfaces of the active material and the conductive agent.3. The lithium secondary battery according to claim 1, wherein theporous membrane is a cellulose non-woven fabric, avinylidenefluoride-hexafluoro-propylene (VdF-HFP) copolymer film, apolyethylene film, a polypropylene film, a double layer ofpolyethylene/polypropylene or a triple layer ofpolypropylene/polyethylene/polypropylene.
 4. The lithium secondarybattery according to claim 1, wherein the fluorine resin includes atleast one selected from the group consisting ofvinylidenefluoride-hexafluoropropylene (VdF-HFP) copolymer andpolyvinylidenefluoride.
 5. The lithium secondary battery according toclaim 1, wherein the crosslinking monomer is at least one selected fromthe group consisting of hexyl acrylate, butyl acrylate,trimethylolpropane triacrylate (TMPTA), butanediol dimethacrylate,diallylsuberate, ethylene glycol dimethacrylate, poly(ethyleneglycol)dimethylacrylate, diglycidyl ester, acrylamide and divinyl benzene. 6.The lithium secondary battery according to claim 1, wherein the fluorineresin comprises a vinylidenefluoride-hexafluoropropylene (VdF-HFP)copolymer.
 7. The lithium secondary battery according to claim 1,further comprising a porous VdF-HFP film interposed between the cathodeand the anode.
 8. The lithium secondary battery according to claim 1,wherein the active material layer in at least one of the cathode andanode infiltrates into at least one of the cathode and anode,respectively.
 9. A lithium secondary battery comprising: a currentcollector, a cathode and an anode having each active material layerformed on the current collector; and a polymer electrolyte interposedbetween the cathode and the anode, wherein a fluorine resin film isformed on at least one surface of the active material layers of thecathode and the anode, a fluorine resin exists in pores betweenconstituents contained in at least one active material layer of thecathode and the anode, the polymer electrolyte is a polymerized productof a crosslinking monomer and an electrolytic solution including alithium salt and an organic solvent, and a porous membrane made of aninsulating resin is interposed between the cathode and the anode, andfurther comprising at least one second crosslinking monomer as thecompound capable of crosslinking with the crosslinking monomer, thesecond crosslinking monomer being at least one selected from the groupconsisting of polyethylene oxide, polyvinylpyrrolidone,polyacrylonitrile, acrylonitrile- methylmethacrylate-styrene terpolymer,vinyl acetate, 2-vinyl-2,3-dioxolane, acrylomorpholine andvinylmethacrylate.
 10. The lithium secondary battery according to claim9, wherein the active material layer includes an active material and aconductive agent, and the fluorine resin exists between the activematerial and the conductive agent and on surfaces of the active materialand the conductive agent.
 11. The lithium secondary battery according toclaim 7, wherein the crosslinking monomer is at least one selected fromthe group consisting of hexyl acrylate, butyl acrylate,trimethylolpropane triacrylate (TMPTA), butanediol dimethacrylate,diallylsuberate, ethylene glycol dimethacrylate, poly(ethyleneglycol)dimethylacrylate, diglycidyl ester, acrylamide and divinyl benzene. 12.The lithium secondary battery according to claim 7, further comprisingat least one second crosslinking monomer as the compound capable ofcrosslinking with the crosslinking monomer, the second crosslinkingmonomer being at least one selected from the group consisting ofpolyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile,acrylonitrile-methylmethacrylate-styrene terpolymer, vinyl acetate,2-vinyl-2,3-dioxolane, acrylomorpholine and vinylmethacrylate.
 13. Thelithium secondary battery according to claim 11, wherein thecrosslinking monomer is at least one selected from the group consistingof hexyl acrylate, butyl acrylate, trimethylolpropane triacrylate(TMPTA), butanediol dimethacrylate, diallylsuberate, ethylene glycoldimethacrylate, poly(ethyleneglycol) dimethylacrylate, diglycidyl ester,acrylamide and divinyl benzene.
 14. The lithium secondary batteryaccording to claim 9, wherein the fluorine resin comprises avinylidenefluoride-hexafluoropropylene (VdF-HFP) copolymer.
 15. Thelithium secondary battery according to claim 9, further comprising aporous VdF-HFP film interposed between the cathode and the anode. 16.The lithium secondary battery according to claim 9, wherein the activematerial layer in at least one of the cathode and anode infiltrates intoat least one of the cathode and anode, respectively.
 17. A lithiumsecondary battery comprising: a current collector, a cathode and ananode having each active material layer formed on the current collector;and a polymer electrolyte interposed between the cathode and the anode,wherein the active material layer in at least one of the cathode andanode comprises a vinylidenefluoride-hexafluoropropylene (VdF-HFP)copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethacrylate,or mixtures thereof, an electrode active material, a conductive agent,and a solvent, and wherein the polymer electrolyte is a polymerizedproduct of a crosslinking monomer and an electrolytic solution, whereinthe crosslinking monomer is at least one selected from the groupconsisting of hexyl acrylate, butyl acrylate, trimethylolpropanetriacrylate (TMPTA), butanediol dimethacrylate, diallylsuberate,ethylene glycol dimethacrylate, poly(ethyleneglycol) dimethylacrylate,diglycidl ester, acrylamide and divinyl benzene.
 18. The lithiumsecondary battery according to claim 17, further comprising a porousVdF-HFP film interposed between the cathode and the anode.
 19. Thelithium secondary battery according to claim 17, wherein the activematerial layer in at least one of the cathode and anode infiltrates intoat least one of the cathode and anode, respectively.
 20. The lithiumsecondary battery according to claim 17, wherein the cathode and/or theanode active material layer comprises avinylidenefluoride-hexafluoropropylene (VdF-HFP) copolymer, an electrodeactive material, a conductive agent, and a solvent.
 21. A lithiumsecondary battery comprising: a current collector, a cathode and ananode having each active material layer formed on the current collector;and a polymer electrolyte interposed between the cathode and the anode,wherein the active material layer in at least one of the cathode andanode comprises a vinylidenefluoride-hexafluoropropylene (VdF-HFP)copolymer. polyvinylidene fluoride, polyacrylonitrile, polymethacrylate,or mixtures thereof, an electrode active material, a conductive agent,and a solvent, and wherein the polymer electrolyte is a polymerizedproduct of a crosslinking monomer and an electrolytic solution, furthercomprising at least one second crosslinking monomer as the compoundcapable of crosslinking with the crosslinking monomer, the secondcrosslinking monomer being at least one selected from the groupconsisting of polyethylene oxide, polyvinylpyrrolidone,polyacrylonitrile, acrylonitrile-methylmethacrylate-styrene terpolymer,vinyl acetate, 2-vinyl-2,3-dioxolane, acrylomorpholine andvinylmethacrylate.